US4468522A - Process for the preparation of (omega-carboalkoxy-nor.alkyl)-dialkylamines - Google Patents

Process for the preparation of (omega-carboalkoxy-nor.alkyl)-dialkylamines Download PDF

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Publication number
US4468522A
US4468522A US06/366,095 US36609582A US4468522A US 4468522 A US4468522 A US 4468522A US 36609582 A US36609582 A US 36609582A US 4468522 A US4468522 A US 4468522A
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diethylamine
process according
palladium
nickel
complexes
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Gian Paolo Chiusoli
Mirco Costa
Luciano Pallini
Giuliana Terenghi
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Assigned to ANIC S.P.A. reassignment ANIC S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CHIUSOLI, GIAN PAOLO, COSTA, MIRCO, PALLINI, LUCIANO, TERENGHI, GIULIANA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid

Definitions

  • This invention relates to a process for the production of (omega-carbalkoxy-nor.alkyl) dialkylamines having a substantially straight linear alkyl chain, which are useful as additives for the industries of the synthetic fibres, for example as viscosity stabilizers for polycaprolactam.
  • olefin compounds the allyl carbon atom of which belongs to a cyclopropane ring which contains one or two carboxyl or carbalkoxy groups on the carbon atom adjacent to the allyl carbon atom, or which is a part of a lactone ring, may, when placed in the presence of specific complexes of palladium or nickel, selectively add dialkylamines to the end carbon atom of the olefin, with a concurrent cleavage of the cyclopropane or lactone ring, thus originating straight-line amine derivatives.
  • a process for the preparation of (omega-carbalkoxyalkyl)-dialkylamines having a substantially straight-line alkyl chain, said process being characterized by comprising the steps of selectively attaching dialkylamines to the end position of an allyl system or of a system which is a part, with its internal carbon atom, of a cyclopropane ring containing one or two carboxyl or carbalkoxy groups on the carbon atom adjacent to the allyl carbon atom, or of a system being a part of a lactone ring, or completely inserted into a lactone ring.
  • R' is either H or COOR
  • R" is H or an alkyl radical containing from 1 to 4 carbon atoms
  • n is an integer from 1 to 3, in the presence of catalysts consisting of triarylphosphine complexes of palladium, or trialkylphosphite complexes of nickel, and subsequently hydrogenating the thus obtained unsaturated amine.
  • the amination of the substrates to be used in the present invention namely 1,1-disubstituted vinylcyclopropane, gamma-vinylbutyro-lactone and the lactone of the 6-hydroxy-4-hexenoic acid, is entirely targeted at the terminal allyl carbon atom, by using, as catalysts, triarylphosphine complexes of palladium or trialkylphosphite complexes of nickel, more particularly tris- or tetrakis-(triphenylphosphine)-palladium, and tris- or tetrakis-(triisopropylphosphite)-nickel.
  • the reaction takes place favourably in solution;
  • the solvent can be composed of the reagents themselves, or of ethereal or esteric solvents, having, if possible, a boiling point temperature below 150° C. (this for questions of cheapness in the separation of the solvents, if any, from the end products).
  • the catalytic complexes used herein permits to achieve high values of catalytic efficiency, inasmuch as it is permissible to use dialkylamine-to-catalyst ratios up to 50,000 and over.
  • dialkylamines in which the alkyl group contained up to 20 carbon atoms, to cyclopropane compounds of the type: ##STR2## wherein R' is H or COOR", and R" is H or an alkyl containing from 1 to 4 carbon atoms, and also to gamma-vinylbutyrolactone and to the lactone of the 6-hydroxy-4-hexenoic acid.
  • a 25-ml flask is charged, in a nitrogen atmosphere, with 0.020 g of Pd(PPh 3 ) 4 . Then, 7 mls of anhydrous and de-aerated tetrahydrofuran are added and, thereafter, 1.94 g of gamma-vinylbutyrolactone and 2.15 g of diethylamine. A yellow homogeneous solution is now formed, which, by means of an oil bath, is maintained at 80° C. for 20 hours. The mixture is allowed to cool and both the excess tetrahydrofuran and diethylamine are removed by evacuation.
  • the oily residue is supplemented with 10 mls of anh.methanol and gaseous hydrogen chloride is bubbled for about two hours through the solution.
  • the solution is evaporated to dryness and the residue is taken up with water, where on the acidic solution is extracted with ethyl ether.
  • the aqueous solution made alkaline with sodium carbonate, is extracted with ethyl ether once again.
  • the ethereal extract essentially contains the compound (5-carbomethoxy)-2-pentenyldiethylamine.
  • Reactions of this kind can be carried out in ethyl acetate or anisole.
  • Example 2 Under the same conditions as in Example 1, a reaction is carried out with 0.008 g of Pd(PPh 3 ) 4 in 7 mls of acetonitrile and 0.780 g of gamma-vinylbutyrolactone, with 0.85 g of diethylamine. By heating to 80° C., there is obtained, after a short time, a homogeneous solution, which is maintained at that temperature (80° C.) for 20 hours.
  • Example 2 Under the same conditions as in Example 1, there are reacted 0.076 g of Ni [P(OisoPr) 3 ] 4 in 10 mls of acetonitrile with 0.30 g of gamma-vinylbutyrolactone and 0.87 g of diethylamine. The reaction mixture is heated to 110° C. for 40 hours. By operating as in Example 1, there are obtained 0.13 g of (5-carbomethoxy-nor.pentyl) diethylamine, corresponding to a yield of 24% relative to the lactone employed, and to a catalytic efficiency of 8 mols of product per mol of nickel complex.
  • Example 2 Under the same conditions as in Example 1, there are reacted without using any solvent 0.052 g of Pd(PPh 3 ) 4 0.91 g of gamma-vinylbutyrolactone and 1.18 g of diethylamine. There are obtained 0.92 g of final hydrogenation product, which corresponds to a yield of 56% relative to the lactone used, and to a catalyst efficiency of 101 mols of product per mol of catalytic complex.
  • Example 4 Under the conditions of Example 4 the lactone of the 6-hydroxy-4-hexenoic acid, which has been prepared together with the vinylbutyrolactone in the ratio of about 1:1 by treating the vinylcyclopropanedicarboxylic ester at 160° C. (bath temperature) under a vacuum of about 1 mm of mercury, and separated by chromatography on silica-gel, is reacted, in an amount of 0.715 g with 0.012 g of Pd(PPh 3 ) 4 , 0.0790 g of Et 2 NH, and 5 mls of tetrahydrofuran for 17 hours at 80° C.
  • Example 2 Under the same conditions of Example 1, there are reacted 0.013 g of Pd(PPh 3 ) 4 with 0.84 g of 1,1-dicarboethoxy-2-vinylcyclopropane and 0.860 g of diethylamine.
  • Example 5 Under the same conditions as in Example 5 there are used 0.005 g of Pd(PPh 3 ) 4 in 3 mls of tetrahydrofuran, 0.63 g of 1,1-dicarboethoxy-2-vinylcyclopropane and 0.56 g of diethylamine.
  • 0.005 g of Pd(PPh 3 ) 4 in 3 mls of tetrahydrofuran 0.63 g of 1,1-dicarboethoxy-2-vinylcyclopropane and 0.56 g of diethylamine.
  • 5-carbomethoxy-nor.pentyl)diethylamine corresponding to a yield of 66% relative to the cyclopropane which has been used and to a catalytic efficiency of 446 mols of product per mol of palladium complex.
  • 0.20 g of the unreacted cyclopropane corresponding to the 32% of that which had been introduced originally.
  • the catalytic efficiency is in the order of magnitude of 4,000 mols per mol of Pd-complex and can be attained after several days at room temperature.
  • Example 5 By operating as in Example 5 there is obtained 0.41 g of (5-carbomethoxy-nor.pentyl) diethylamine, which corresponds to a yield of 83% on the originally fed cyclopropane and to a catalytic efficiency of 210 mols per mol of palladium complex. Similar results can be obtained when operating with 1,1-dicarboxy-2-vinylcyclopropane in lieu of the corresponding diester.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US06/366,095 1981-04-10 1982-04-06 Process for the preparation of (omega-carboalkoxy-nor.alkyl)-dialkylamines Expired - Fee Related US4468522A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT21030/81A IT1167735B (it) 1981-04-10 1981-04-10 Procedimento per la preparazione di (omeg-carbalcossi-n-alchil)-dialchilammine
IT21030A/81 1981-04-10

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US4468522A true US4468522A (en) 1984-08-28

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EP (1) EP0078067B1 (it)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020155378A1 (en) * 2001-02-19 2002-10-24 Yasunori Uetani Chemical amplifying type positive resist compositions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682160A (en) * 1948-10-18 1952-11-05 Wellcome Found Improvements in and relating to the preparation of substituted aminoalcohols, alkenylamines, aminoalkanes and quaternary salts thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB653452A (en) * 1947-04-12 1951-05-16 Goodrich Co B F Improvements in or relating to a method of preparing an (n,n-diaryl) amino acid ester
US4035409A (en) * 1974-12-18 1977-07-12 Texaco Inc. Hydrocarbyl amine substituted propionic ester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB682160A (en) * 1948-10-18 1952-11-05 Wellcome Found Improvements in and relating to the preparation of substituted aminoalcohols, alkenylamines, aminoalkanes and quaternary salts thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020155378A1 (en) * 2001-02-19 2002-10-24 Yasunori Uetani Chemical amplifying type positive resist compositions

Also Published As

Publication number Publication date
IT1167735B (it) 1987-05-13
EP0078067A1 (en) 1983-05-04
DE3266988D1 (en) 1985-11-28
IT8121030A1 (it) 1982-10-10
EP0078067B1 (en) 1985-10-23
IT8121030A0 (it) 1981-04-10

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Effective date: 19880828